Tertiary hydroxyl carboxaldehydes, organoleptic uses thereof, and processes for producing same

ABSTRACT

Described are tertiary hydroxyl carboxaldehydes defined according to the generic structure: ##STR1## wherein the lines ##STR2## represent covalent carbon-carbon bonds when m does not=0; and wherein the lines ##STR3## do not represent any bonds when m=0; wherein R represents hydrogen or methyl; wherein p and q each represents 0 or 1 with the proviso that p=1 when q=0 and p=0 when q=1; wherein X and Z each represent one or more carbon atoms required to complete a bicyclo ring with the lines ##STR4## representing carbon-carbon bonds; wherein X and Z complete a phenyl moiety when the line ##STR5## represents no bond; wherein X and Z complete a cycloalkyl ring moiety with the lines ##STR6## represent carbon-carbon bonds and with the line ##STR7## representing no bond; and wherein when m is 0, X represents an alkylene moiety, processes for preparing same by means of reacting carbon monoxide and hydrogen with an unsaturated tertiary alcohol defined according to the structure: ##STR8## by means of an oxo reaction, and uses thereof in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles (e.g., cosmetic powders, perfumed polymers, solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, fabric softener articles, hair preparations, face creams, and the like).

BACKGROUND OF THE INVENTION

This is a divisional of application Ser. No. 656,661, filed 10/1/84,which, in turn, is a divisional of application for U.S. Letters Patent,Ser. No. 511,965, filed on 7/8/83, now U.S. Pat. No. 4,491,537 issued1/1/85.

This invention relates to tertiary hydroxyl carboxaldehydes definedaccording to the structure: ##STR9## wherein the lines ##STR10##represent covalent carbon-carbon bonds when m does not=0; and whereinthe lines ##STR11## do not represent any bonds when m=0; wherein Rrepresents hydrogen or methyl; wherein p and q each represents 0 or 1with the proviso that p=1 when q=0 and p=0 when q=1; wherein X and Zeach represent one or more carbon atoms required to complete a bicycloring with the lines ##STR12## representing carbon-carbon bonds; whereinX and Z complete a phenyl moiety when the line ##STR13## represents nobond; wherein X and Z complete a cycloalkyl ring moiety with the lines##STR14## represent carbon-carbon bonds and with the line ##STR15##representing no bond; and wherein when m is 0, X represents an alkylenemoiety, produced according to an oxo reaction on a member of theunsaturated genus having the structure: ##STR16## and organoleptic usesthereof particularly augmenting or enhancing the aroma of perfumecompositions, colognes and perfumed articles.

Inexpensive chemical compounds which can provide woody, nutty, floral,lilac, green, peach-like, balsamic and fresh air dried linen aromas withminty, floral, cinnamon-like and green topnotes are highly desirable inthe art of perfumery. Many of the natural materials which provide suchfragrances and contribute such desired nuances to perfumery compositionsand perfumed articles are high in cost, unobtainable at times, vary inquality from one batch to another and/or are generally subject to theusual variations of natural products.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthe synthetic materials either have the desired nuances only to arelatively small degree, or they contribute undesirable or unwanted odorto the compositions.

U.S. Pat. No. 4,357,247 issued on Nov. 2, 1982 discloses aliphatic C₁₁branched chain aldehydes and alcohols, defined according to the genericstructure: ##STR17## wherein one of X₁ or X₂ is hydrogen and the otherof X₁ or X₂ is methyl; and wherein one of Z₁ or Z₂ is hydrogen and theother of Z₁ or Z₂ is hydroxymethyl having the structure: ##STR18## orcarboxaldehyde having the structure: ##STR19## for use in augmenting orenhancing the aroma of perfume compositions, colognes and perfumedarticles. The resulting compounds and compositions of matter providecitrusy, green, melony, woody, peanut oil-like and vetiver-like aromanuances. The compounds of U.S. Pat. No. 4,357,247 are different in kindinsofar as their structure and organoleptic properties are concernedfrom the compounds of the instant application.

Furthermore, C₁₁ aliphatic alcohols and aldehydes are well known in theart of perfumery, e.g., n-undecanal and n-undecanol. Oxo reactionproducts on hydrocarbon compounds are also well known in the perfumeryindustry aside from U.S. Pat. No. 4,357,247. Thus, U.S. Pat. No.4,146,505 discloses the formation ofhydroxymethyl-formyl-tricyclo[5,2,1,0²,6 ]decane having the structure:##STR20## wherein R₁ and R₂ are the hydroxymethyl group, CH₂ OH or theformyl group CHO and R₁ represents CH₂ OH when R₂ is CHO and vice versa.This polycyclic carboxaldehyde alcohol is indicated to be useful as amusk aroma imparting or augmenting material. The material is indicatedto be produced by reaction of carbon monoxide and hydrogen withdicyclopentadiene. Other oxo reaction products on unsaturatedhydrocarbons are known in the perfumery industry, for example,"Vandor-B", which is the oxo reaction product of carbon monoxide andhydrogen on diiosbutylene. This material has been produced byInternational Flavors & Fragrances Inc., the assignee of the instantpatent application, for several years.

Nothing in the prior art however, discloses the compounds definedaccording to the structure: ##STR21## produced by oxo reaction oncompounds defined according to the structure: ##STR22## wherein thelines ##STR23## represent covalent carbon-carbon bonds when m doesnot=0; and wherein the lines ##STR24## do not represent any bonds whenm=0; wherein R represents hydrogen or methyl; wherein p and q eachrepresents 0 or 1 with the proviso that p=1 when q=0 and p=0 when q=1;

wherein X and Z each represent one or more carbon atoms required tocomplete a bicyclo ring with the lines ##STR25## representingcarbon-carbon bonds; wherein X and Z complete a phenyl moiety when theline ##STR26## represents no bond; wherein X and Z complete a cycloalkylring moiety with the lines ##STR27## represent carbon-carbon bonds andwith the line ##STR28## representing no bond; and wherein when m is 0, Xrepresents an alkylene moiety.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for fraction 6 of the distillation product ofthe reaction product containing the compounds having the structures:##STR29##

FIG. 2 is the NMR spectrum for the peak indicated by reference numeral"11" of the GLC profile of FIG. 1 for the compound having the structure:##STR30## (Conditions: Field strength 100 MHz; Solvent: CFCl₃).

FIG. 3 is the NMR spectrum for the peak indicated by reference numeral"12" of the GLC profile of FIG. 1 for the compound having the structure:##STR31## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 4 is the NMR spectrum for the peak indicated by reference numeral"13" of the GLC profile of FIG. 1 containing the compounds having thestructures: ##STR32## (Conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 5 is the GLC profile for the crude reaction product producedaccording to Example II containing the compounds having the structures:##STR33##

FIG. 6 is the GLC profile for Fraction 1 of the re-distillation productof Example II containing the compounds defined according to thestructures: ##STR34##

FIG. 7 is the NMR spectrum for a mixture of compounds having thestructures: ##STR35## produced according to Example II. (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 8 is the infra-red spectrum for the mixture of compounds having thestructures: ##STR36## produced according to Example II.

FIG. 9 is the GLC profile for bulked fractions 5 and 6 of the firstdistillation of the reaction product of Example III containing thecompound having the structure: ##STR37##

FIG. 10 is the NMR spectrum for Fraction 6 of the first distillation ofthe reaction product of Example III containing the compound having thestructure: ##STR38## (Conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 11 is the infra-red spectrum for Fraction 6 of the firstdistillation of the reaction product of Example III containing thecompound having the structure: ##STR39##

FIG. 12 is the GLC profile for the crude reaction product of Example IVcontaining the compounds defined according to the structures: ##STR40##

FIG. 13 is the GLC profile for Fraction 6 of the second distillation ofExample IV containing the compound having the structure: ##STR41##

FIG. 14 is the NMR spectrum for Fraction 4 of the second distillation ofExample IV containing the compound having the structure: ##STR42## (75%)and the compound having the structure: ##STR43## (25%). (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for fraction 6 of the distillation product ofthe reaction product of Example I. The peak indicated by referencenumeral "11" is the peak for the compound having the structure:##STR44## The peak indicated by reference numeral "12" is the peak forthe compound having the structure: ##STR45## The peak indicated byreference numeral "13" is the peak for the compound having thestructure: ##STR46## in admixture with the compound having thestructure: ##STR47## (conditions of GLC operation: Carbowax columnprogrammed at 100°-220° C., isothermal).

FIG. 5 is the GLC profile for the crude reaction product of Example II.The peak indicated by reference numeral "51" is the peak for the mixtureof compounds defined according to the structures: ##STR48## The peakindicated by reference numeral "52" is the peak for the startingmaterial having the structure: ##STR49## The peak indicated by referencenumeral "53" is the peak for the reaction solvent, toluene.

FIG. 12 is the GLC profile for the crude reaction product of Example IV.The peak indicated by reference numerals "122" and "123" are the peaksfor the compounds defined according to the structures: ##STR50## Thepeak indicated by reference numeral "121" is the peak for the reactionsolvent, toluene.

THE INVENTION

It has now been determined that tertiary hydroxyl carboxaldehydesdefined according to the generic structure: ##STR51## wherein the lines##STR52## represent covalent carbon-carbon bonds when m does not=0; andwherein the lines ##STR53## do not represent any bonds when m=0; whereinR represents hydrogen or methyl; wherein p and q each represents 0 or 1with the proviso that p=1 when q=0 and p=0 when q=1; wherein X and Zeach represent one or more carbon atoms required to complete a bicycloring with the lines ##STR54## representing carbon-carbon bonds; whereinX and Z complete a phenyl moiety when the line ##STR55## represents nobond; wherein X and Z complete a cycloalkyl ring moiety with the lines##STR56## represent carbon-carbon bonds and with the line ##STR57##representing no bond; and wherein when m is 0, X represents an alkylenemoiety, are capable of imparting, augmenting or enhancing a variety offragrances in or to consumable materials.

Briefly, our invention contemplates augmenting or enhancing fragrancesof such consumable materials as perfumes, perfumed articles, (e.g.,solid or liquid anionic, cationic, nonionic or zwitterionic detergents,cosmetic powders, fabric softener compositions, drier-added fabricsoftener articles and perfumed polymers) and colognes by adding theretoa small, but effective, amount of at least one of the compounds definedaccording to the generic structure: ##STR58## wherein the lines##STR59## represent covalent carbon-carbon bonds when m does not=0; andwherein the lines ##STR60## do not represent any bonds when m=0; whereinR represents hydrogen or methyl; wherein p and q each represents 0 or 1with the proviso that p=1 when q=0 and p=0 when q=1; wherein X and Zeach represent one or more carbon atoms required to complete a bicycloring with the lines ##STR61## representing carbon-carbon bonds; whereinX and Z complete a phenyl moiety when the line ##STR62## represents nobond; wherein X and Z complete a cycloalkyl ring moiety with the lines##STR63## represent carbon-carbon bonds and with the line ##STR64##representing no bond; and wherein when m is 0, X represents an alkylenemoiety.

More specifically, the structures of the compounds useful in practicingour invention are as follows: ##STR65##

The tertiary hydroxyl carboxaldehydes of our invention augment orenhance woody, nutty, floral, lilac, peach-like, green, balsamic andfresh air dried linen aromas adding thereto minty, floral, cinnamon-likeand green topnotes to perfumes, perfumed articles and colognes therebycausing one or more of said tertiary hydroxyl carboxaldehydes to beuseful particularly in vetiver type and "fresh air dried linen" typefragrances.

The tertiary hydroxyl carboxaldehydes of our invention may be preparedby first (i) reacting unsaturated compounds defined according to thegeneric structure: ##STR66## with carbon monoxide and hydrogen in thepresence of a "oxo" reaction catalyst according to the reaction:##STR67## wherein the lines ##STR68## represent covalent carbon-carbonbonds when m does not=0; and wherein the lines ##STR69## do notrepresent any bonds when m=0; wherein R represents hydrogen or methyl;wherein p and q each represents 0 or 1 with the proviso that p=1 whenq=0 and p=0 when q=1; wherein X and Z each represent one or more carbonatoms required to complete a bicyclo ring with the lines ##STR70##representing carbon-carbon bonds; wherein X and Z complete a phenylmoiety when the line ##STR71## represents no bond; wherein X and Zcomplete a cycloalkyl ring moiety with the lines ##STR72## representcarbon-carbon bonds and with the line ##STR73## representing no bond;and wherein when m is 0, X represents an alkylene moiety. The reactionis carried out at temperatures of between 110° C. and 300° C. atpressures of between 15 and 250 atmospheres; with the ratio of partialpressure of carbon monoxide:hydrogen being from 0.1:1 up to 1:0.1. Anyoxo type reaction catalyst may be used, but, most preferably, thecatalyst to yield the best perfume mixtures are as follows:

Dicobalt octacarbonyl;

Cobalt octanoate;

Palladium chloride;

Rhodium trichloride;

Iron pentacarbonyl;

Nickel tetracarbonyl;

Polymer-bonded rhodium catalyst (e.g., rhodium bonded on a polystyrenesubstrate);

Tris-triphenyl phosphine rhodium-1-chloride;

Rhodium acetoacetate dicarbonyl;

Rhodium-acetoacetate-triphenylphosphene.

Depending upon the conditions of reaction including, temperature,partial pressures of carbon monoxide and hydrogen, mole ratio of alcoholhaving the structure: ##STR74## to catalyst, concentration of alcoholhaving the structure: ##STR75## in solvent, concentration of catalyst insolvent and time of reaction, the nature of the isomers of the aldehydesdefined according to the structure: ##STR76## wherein the lines##STR77## represent covalent carbon-carbon bonds when m does not=0; andwherein the lines ##STR78## do not represent any bonds when m=0; whereinR represents hydrogen or methyl; wherein p and q each represents 0 or 1with the proviso that p=1 when q=0 and p=0 when q=1; wherein X and Zeach represent one or more carbon atoms required to complete a bicycloring with the lines ##STR79## representing carbon-carbon bonds; whereinX and Z complete a phenyl moiety when the line ##STR80## represents nobond; wherein X and Z complete a cycloalkyl ring moiety with the lines##STR81## represent carbon-carbon bonds and with the line ##STR82##representing no bond; and wherein when m is 0, X represents an alkylenemoiety will vary. The variation of the conditions of reaction is afunction of the nature of the perfumery product desired. Accordingly,the organoleptic qualities of the product desired can be varied in atailor-made fashion as a function of the conditions of the reaction.

Exemplary of the reactants and products produced in their organolepticproperties are the following:

                                      TABLE I                                     __________________________________________________________________________    Alcohol Reactant           Aldehyde Reaction Product                                                                      Organoleptic                      __________________________________________________________________________                                                Property                           ##STR83##                                                                                                ##STR84##       A woody and nutty aroma with                                                  minty and floral topnotes.                                    ##STR85##                                                                    and                                                                            ##STR86##                                          ##STR87##                                                                                                ##STR88##       A floral (lilac) aroma with                                                   cinnamon-like topnotes.                                      and                                                                            ##STR89##                                          ##STR90##                                                                                                ##STR91##       A green, woody, peach- like                                                   and balsamic aroma profile                                                    with green floral topnotes.        ##STR92##                 A mixture of compounds having the                                                              A fresh air dried linen                                                       aroma.                                                 ##STR93##                                                                    and                                                                            ##STR94##                                                __________________________________________________________________________

As olfactory agents, the tertiary hydroxyl carboxaldehydes taken aloneor in admixture, of our invention, can be formulated into, or used ascomponents of a "perfume composition" or can be used as components of a"perfumed article", or the perfume composition may be added to perfumedarticles.

The term "perfume composition" is used herein to mean a mixture oforganic compounds including, for example, mono alcohols, aldehydes(other than the tertiary hydroxyl carboxaldehydes of our invention),ketones, nitriles, ethers, lactones, natural essential oils, syntheticessential oils and hydrocarbons which are admixed so that the combinedodors of the individual components produce a pleasant or desiredfragrance. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the compositions; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation, and substances which retardevaporation; and (d) topnotes which are usually low boiling,fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effects of each of theingredients and in certain instances, a synergistic effect as a resultof the addition of certain ingredients. Thus, the individual compoundsof this invention, or mixtures thereof, can be used to alter the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition.

The amount of the tertiary hydroxyl carboxaldehydes of our inventionwhich will be effective in perfume compositions depends on many factors,including the other ingredients, their amounts and the effects which aredesired. It has been found that perfume compositions containing aslittle as 0.05% of the tertiary hydroxyl carboxaldehydes of thisinvention, or even less, can be used to impart an interesting, woody,nutty, floral, lilac, green, peach-like, balsamic and fresh air driedlinen aromas with minty, floral, cinnamon-like and green topnotes tosoaps, liquid or solid anionic, cationic, nonionic or zwitterionicdetergents, cosmetics, cosmetic powders, liquid and solid fabricsofteners, drier-added fabric softener articles, (e.g., BOUNCE® aregistered trademark of the Procter & Gamble Company of Cincinnati,Ohio), optical brightener compositions and other products. The amountemployed can range up to 70% or even higher, and will depend onconsiderations of cost, nature of the end product, and the effectdesired on the finished product and particular fragrance sought. Thus,for example, when fragrancing liquid bleach compositions containingalkalihypochlorite such as, for example, sodium hypochlorite, forexample CLOROX®, (registered trademark of Clorox, Inc.), the amountemployed can be as high as 100% of the fragrance involved in the liquidbleach. Indeed, a distinctive aspect of our invention is the use of oneor more of the tertiary hydroxyl carboxaldehydes of our invention in astable liquid bleach composition.

The tertiary hydroxyl carboxaldehydes of this invention, taken alone orin admixture, can be used alone, or in a perfume composition as anolfactory component in detergents, soaps, space odorants and deodorants;perfumes; colognes, toilet waters; bath salts; hair preparations, suchas lacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as creams, deodorants, hand lotions, sunscreens; powders, such astalcs, dusting powders, face powders and the like; liquid bleaches, suchas sodium hypochlorite-containing bleaches; floor waxes; automobilearomas and automobile polish compositions; and perfumed polymers andperfumed polymer articles of manufacture such as perfumed garbage bags.

When used as an olfactory component of a perfumed article, as little as0.01% of one or more of the tertiary hydroxyl carboxaldehydes of ourinvention will suffice to impart an interesting, woody, nutty, floral,lilac, green, peach-like, balsamic and fresh air dried linen aromas withminty, floral, cinnamon-like and green topnotes. Generally, no more than0.5% is required to impart such aromas, however, in view of the ratherlow cost of the tertiary hydroxyl carboxaldehydes of our invention, upto 100% of the perfume composition can be one or more of the tertiaryhydroxyl carboxaldehydes of our invention.

Accordingly, the range of use in perfumed articles of the tertiaryhydroxyl carboxaldehydes of our invention is from about 0.01% up toabout 0.5%.

In addition, the perfume composition of our invention can contain avehicle or carrier for the tertiary hydroxyl carboxaldehydes takenalone, or taken together with other ingredients. The vehicle can be aliquid such as a non-toxic alcohol such as ethanol, a glycol such aspropylene glycol, or the like. The carrier can be an absorbent solid,such as a gum or components (e.g., gum arabic, xanthan gum or guar gumor combinationa thereof) or components for encapsulating the compositionsuch as gelatin which can be used to form a capsule wall surrounding theperfume oil, as by means of coacervation, or a polymer such as theureformaldehyde polymer which can be used to surround a perfume liquidcenter.

It will thus be apparent that the tertiary hydroxyl carboxaldehydes ofour invention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties such as fragrances of awide variety of consumable materials.

The following examples serve to illustrate our invention, and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of 8-Hydroxy-p-Methane-2-Carboxaldehyde

Reaction: ##STR95##

Into a high pressure autoclave in placed 1232 grams (8 moles) ofterpinol having the structure: ##STR96## and 0.45 grams of rhodium acetoacetate-dicarbonyl. The autoclave is sealed and pressurized to 1000 psigand heated to a temperature of 150°-160° C. with a 50:50 mole:molemixture of carbon monoxide and hydrogen. The autoclave contents aremaintained at a pressure of 1000 psig and a temperature in the range of150°-160° C. for a period of forty one hours.

At the end of this time period, the autoclave contents are cooled andthe contents are removed from the autoclave filtered and distilled on a1" splash column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         /74          /100    4:0                                            2          88          110     5:5                                            3          94          115     5:5                                            4         105          130     5:5                                            5         128          130     5:5                                            6         124          158     2:6                                            7         149          220     2:6                                            ______________________________________                                    

Fractions 2-7 are bulked and redistilled on an 18" Goodloe columnyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         78/83   118/124   3:2/3:3                                                                              11.2                                       2          82     127       2:7    14.9                                       3          83     129       2:7    12.5                                       4          83     135       3:6    14.1                                       5         119     135       3:0    25.3                                       6         123     137       3:0    25.8                                       7         123     137       3:0     6.7                                       8         128     144       3:0    12.1                                       9         128     145       3:2     9.6                                       10        127     150       3:2    19.9                                       11        130     162       3:4    15.0                                       12        131     181       3:8     8.5                                       13        128     188       3:6     2.4                                       ______________________________________                                    

Fractions 8-10 are bulked and determined to have a woody and nutty aromawith minty and floral topnotes.

FIG. 1 is the GLC profile of Fraction 6 of the foregoing distillation.(Conditions: Carbowax column programmed at 100°-220° C. isothermal). Thepeak indicated by reference numeral "11" is the peak for the compoundhaving the structure: ##STR97## The peak indicated by reference numeral"12" is the peak for the compound having the structure: ##STR98##

The peak indicated by reference numeral "13" is the peak for the mixtureof compounds defined according to the structure: ##STR99##

FIG. 2 is the NMR spectrum for the peak indicated by reference numeral"11" on FIG. 1 for the compound defined according to the structure:##STR100## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 3 is the NMR spectrum for the peak indicated by reference numeral"12" on the GLC profile of FIG. 1 for the compound having the structure:##STR101## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 4 is the NMR spectrum for the peak indicated by reference numeral"13" on the GLC profile of FIG. 1 and is for a mixture of compoundsdefined according to the structures: ##STR102##

EXAMPLE II Preparation of 5-(1-Hydroxy-1-Methylethyl)-6,6-Dimethyl-(1and 2) Norbornane Carboxaldehyde

Reaction: ##STR103##

Into a 500 cc autoclave is placed 205.5 grams of the compound having thestructure: ##STR104## 0.1 grams of rhodium aceto acetate and 7 grams oftriphenyl phosphine, and 100 cc toluene.

The autoclave is sealed and pressurized to 1000 psig and heated to atemperature of 120° C. using a 50:50 mole:mole mixture of carbonmonoxide and hydrogen. The autoclave contents are maintained at 1000psig and 120° C. for a period of four hours.

At the end of the four hour period, the autoclave contents are cooledand the autoclave is opened and the contents are filtered and thendistilled through a 2" splash column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         26/94        48/129  1:8/0:75                                       2          99          129     0:7                                            3         125          139     2:1                                            4         104          138      0:55                                          5         132          142     2:1                                            6         126          198     2:2                                            ______________________________________                                    

Fractions 2-6 are then bulked and redistilled on an 18" Goodloe columnyielding the following fractions:

    ______________________________________                                                 Vapor    Liquid     Vacuum Weight                                    Fraction Temp.    Temp.      mm/Hg. of                                        No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             Fraction                                  ______________________________________                                        1        128/135  147/148    3:5/3:6                                                                               8.1                                      2        137      149        3:3    14.1                                      3        140      150        3:7    13.4                                      4        140      149        3:4    15.0                                      5        140      152        3:4    31.2                                      6        140      150        3:4    15.9                                      7        140      150        3:4    26.4                                      8        140      154        3:4    19.7                                      9        140      175        3:4    13.4                                      10       135      230        3:4    10.3                                      ______________________________________                                    

Fractions 5-8 are bulked and the bulked fractions have a floral (lilac)aroma with cinnamon-like topnotes.

FIG. 5 is the GLC profile for the crude reaction product prior todistillation. The peak indicated by reference numeral "51" is the peakfor the mixture of compounds defined according to the structures:##STR105##

The peak indicated by reference numeral "52" is the peak for the staringmaterial having the structure: ##STR106##

The peak indicated by reference numeral "53" is the peak for thereaction solvent, toluene.

FIG. 6 is the GLC profile for Fraction 1 of the redistillation.

FIG. 7 is the NMR spectrum for the mixture of compounds having thestructures: ##STR107## produced according to this example. (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 8 is the infra-red spectrum for the mixture of compounds having thestructures: ##STR108## produced according to this example.

EXAMPLE III Preparation ofp-(1-Hydroxy-1-Methylethyl)-β-Methyl-Hydrocinnamaldehyde

Reaction: ##STR109## Into a 700 cc autoclave is placed the followingingredients: (i) 110 grams p-isopropyl phenyl dimethyl carbinol havingthe structure: ##STR110## (ii) 8 grams--triphenyl phosphine; (iii) 0.1grams--rhodium aceto acetate;

(iv) 300 ml--toluene

The autoclave is closed and pressured with a 50:50 mole:mole mixture ofcarbon monoxide and hydrogen to a pressure of 1000 psig and heated to atemperature in the range of 120°-150° C. and maintained at 120°-150° C.and at a pressure of 1000 psig for a period of fifteen hours.

At the end of the fifteen hour period, the autoclave is cooled andopened and the contents are filtered. The resulting filtrate is thendistilled through a 6" Miller column yielding the following fractions:

    ______________________________________                                                  Vapor        Liquid  Vacuum                                         Fraction  Temp.        Temp.   mm/Hg.                                         No.       (°C.) (°C.)                                                                          Pressure                                       ______________________________________                                        1         /24          /27     1:0                                            2          24           31     2:1                                            3          25           87     1:0                                            4         108          152     0:5                                            5         122          154     0:5                                            6         130          200     0:5                                            ______________________________________                                    

Fractions 5-6 are bulked and redistilled on an 18" Goodloe columnyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         /65     /165      2:3    2.5                                        2         94      156       2:3    5.7                                        3         55      158       2:4    5.3                                        4         80      156       2:3    7.4                                        5         82      157       2:2    7.9                                        6         113     163       2:0    8.6                                        7         120     168       2:0    12.0                                       8         106     187       2:0    7.3                                        9         53      200       2:0    9.4                                        ______________________________________                                    

Fractions 5-8 are bulked. The bulked fractions have an interestinggreen, woody, peach-like and balsamic aroma profile with green andfloral topnotes.

FIG. 9 is the GLC profile of bulked Fractions 5-6 of the firstdistillation.

FIG. 10 is the NMR spectrum for Fraction 6 of the first distillationcontaining the compound having the structure: ##STR111## (Conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 11 is the infra-red spectrum for Fraction 6 of the firstdistillation containing the compound having the structure: ##STR112##

EXAMPLE IV Preparation of 12-Hydroxy-12-Methyl Tridecanal

Reaction: ##STR113## Into a 1000 cc autoclave is placed the followingingredients: (i) 302 grams of the alcohol having the structure:##STR114## (ii) 0.1 grams of rhodium aceto acetate; (iii) 6.5 grams oftriphenylphosphine;

(iv) 200 ml--toluene.

The autoclave is sealed and the pressure is increased to 700 psig usinga 50:50 mole:mole mixture of carbon monoxide and hydrogen. Thetemperature of the contents in raised to a 120°-140° C. and maintainedat a temperature of 120°-140° C. at a pressure of 700 psig for a periodof twenty five hours. At the end of the twenty five hour period, theautoclave is cooled and the contents are filtered. The filtrate is thendistilled on a 2" splash column yielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1         /132    /160      3:6     1.3                                       2         154     167       4:8    26.8                                       3         150     162       3:0    96.7                                       4         152     162       1:6    77.3                                       5         152     260       3:0    101.6                                      ______________________________________                                    

Fractions 2-5 are bulked and redistilled on a 18" Goodloe columnyielding the following fractions:

    ______________________________________                                                  Vapor   Liquid    Vacuum Weight                                     Fraction  Temp.   Temp.     mm/Hg. of                                         No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             Fraction                                   ______________________________________                                        1          142/    160/     2:0     7.2                                       2         145     162       7:0    23.8                                       3         146     162       2:0    30.5                                       4         146     163       2:0    30.2                                       5         146     165       2:0    29.3                                       6         146     167       2:0    19.0                                       7         146     170       2:0    21.4                                       8         146     180       2:0    18.6                                       9         146     195       2:0    13.4                                       10        144     230       2:0     9.9                                       11        140     245       2:0     3.4                                       ______________________________________                                    

Fractions 4-8 of the foregoing distillation are bulked and have a freshair dried linen aroma.

FIG. 12 is the GLC profile for the crude reaction product prior to thefirst distillation. The peaks indicated by reference numerals "122" and"123" are the peaks for the compounds defined according to thestructures: ##STR115##

The peak indicated by reference numeral "121" is the peak for thetoluene solvent used in the reaction mass.

FIG. 13 is the GLC profile for Fraction 6 of the second distillation.

FIG. 14 is the NMR spectrum for Fraction 4 of the second distillation(conditions: Field strength: 100 MHz; Solvent: CFCl₃). This materialcontains 25% by weight of the compound having the structure: ##STR116##and 75% by weight of the compound having the structure: ##STR117##

EXAMPLE V Preparation of Pine Formulation

The following pine formulations are prepared:

    ______________________________________                                        Ingredients          V-A    V-B    V-C  V-D                                   ______________________________________                                        Isoburnyl acetate    100    100    100  100                                   Camphor              10     10     10   10                                    Terpineol            25     25     25   25                                    Fir balsam absolute  20     20     20   20                                    (50% in diethyl phthalate)                                                    Coumarin             4      4      4    4                                     Linalool             30     30     30   30                                    Anethol              2      2      2    2                                     Fenchyl alcohol      10     10     10   10                                    Lemon terpenes washed                                                                              50     50     50   50                                    Borneol              5      5      5    5                                     Galbanum oil         5      5      5    5                                     Turpentine Russian   150    150    150  150                                   Pinus pumilionus     50     50     50   50                                    Eucalyptol           50     50     50   50                                    2,2,6-trimethyl-1-cyclohexene-                                                                     5      5      5    5                                     1-carboxaldehyde                                                              Maltol (1% in diethyl                                                                              5      5      5    5                                     phthalate)                                                                    Bulked Fractions 8-10 of                                                                           479    000    000  000                                   the distillation product                                                      of Example I containing                                                       the compounds having the                                                      structures:                                                                    ##STR118##                                                                   Mixture of compounds 0      479    0    0                                     having the structures:                                                         ##STR119##                                                                   produced according to                                                         Example II, bulked                                                            Fractions 5-8                                                                 Compound having the  0      0      479  0                                     structure:                                                                     ##STR120##                                                                   produced according to                                                         Example III, bulked                                                           Fractions 5-8                                                                 Mixture of compounds 0      0      0    479                                   having the structures:                                                         ##STR121##                                                                   prepared according to                                                         Example IV, bulked                                                            distillation                                                                  Fractions 4-8                                                                 ______________________________________                                    

The perfume formulation containing the mixture of compounds having thestructures: ##STR122## can be described as "piney having woody and nuttyundertones and minty and floral topnotes".

The formulation containing the mixture of compounds defined according tothe structures: ##STR123## produced according to Example II can bedescribed as "piney having lilac undertones and floral (lilac-like) andcinnamon-like topnotes".

The formulation containing the compound having the structure: ##STR124##produced according to Example III can be described as "piney with green,woody, peach-like and balsamic undertones and green, floral topnotes".

The formulation containing the mixture of compounds having thestructures: ##STR125## produced according to Example IV can be describedas "piney with a fresh air dried linen-like undertone".

EXAMPLE VI Preparation of Cosmetic Powder Compositions

Cosmetic powder compositions are prepared by mixing in a ball mill, 100grams of talcum powder (per compositions) with 0.25 grams of thesubstance set forth in Table II below (per composition). Each of thecosmetic powder compositions has an excellent aroma as described inTable II below:

                  TABLE II                                                        ______________________________________                                        Substance            Aroma Description                                        ______________________________________                                        Mixture of compounds having                                                                        A woody, nutty aroma                                     the structures:      with minty and floral                                                         topnotes.                                                 ##STR126##                                                                   produced according to                                                         Example I, bulked                                                             distillation                                                                  Fractions 4-6.                                                                Mixture of compounds A floral (lilac) aroma                                   having the structures:                                                                             with floral (lilac-like)                                                      and cinnamon-like top-                                                        notes.                                                    ##STR127##                                                                   produced according to                                                         Example II, bulked                                                            distillation                                                                  Fractions 5-8                                                                 Compound having the  A green, woody, peach-                                   structure:           like and balsamic aroma                                                       with green and floral                                                         topnotes.                                                 ##STR128##                                                                   produced according to                                                         Example III, bulked                                                           distillation                                                                  Fractions 5-8                                                                 Mixture of compounds A fresh air dried                                        having the structures:                                                                             linen aroma.                                              ##STR129##                                                                   produced according to                                                         Example IV, bulked                                                            distillation                                                                  Fractions 4-8                                                                 Perfume composition of                                                                             Piney, having woody                                      Example V-A          and nutty undertones                                                          and minty and floral                                                          topnotes.                                                Perfume composition of                                                                             Piney, having lilac                                      Example V-B          undertones and floral                                                         (lilac-like) and cinna-                                                       mon-like topnotes.                                       Perfume composition of                                                                             Piney, with green,                                       Example V-C          woody, peach-like and                                                         balsamic undertones and                                                       green, floral topnotes.                                  Perfume compositions of                                                                            Piney, with a fresh air                                  Example V-D          dried linen-like under-                                                       tone.                                                    ______________________________________                                    

EXAMPLE VII Perfumed Liquid Detergents

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976 incorporated by reference herein) with aroma nuances as setforth in Table II of Example VI, are prepared containing 0.10%, 0.15%,0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in Table II ofExample VI. They are prepared by adding and homogeneously mixing theappropriate quantity of substance set forth in Table II of Example VI inthe liquid detergent. The detergents all possess excellent aromas as setforth in Table II of Example VI, the intensity increasing with greaterconcentrations of substance as set forth in Table II of Example VI.

EXAMPLE VIII Preparation of Colognes and Handkerchief Perfumes

Compositions as set forth in Table II of Example VI are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table II ofExample VI are imparted to the colognes and to the handkerchief perfumesat all levels indicated.

EXAMPLE IX Preparation of Soap Compositions

One hundred grams of soap chips (per sample) (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table II of Example VI untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example VI.

EXAMPLE X Preparation of Solid Detergent Compositions

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated herein byreference):

    ______________________________________                                        Ingredient          Percent by Weight                                         ______________________________________                                        Neodol ® 45-11 (a C.sub.14 -C.sub.15                                                          12                                                        alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                   Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

The detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table II of Example VI. Each ofthe detergent samples has an excellent aroma as indicated in Table II ofExample VI.

EXAMPLE XI

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate Coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table II of Example VI.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table II of Example VI, supra, consist of a substrate coating havinga weight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table II of Example VI isadmixed in each case with the outer coating mixture, thereby providing atotal aromatized outer coating weight ratio to substrate of about 0.5:1by weight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a dryer on operation thereof ineach case using said drier-added fabric softener non-woven fabrics andthese aroma characteristics are described in Table II of Example VI,supra.

EXAMPLE XII Hair Spray Formulation

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol,8.0 grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                        Dioctyl sebacate  0.05 weight percent                                         Benzyl alcohol    0.10 weight percent                                         Dow Corning 473 fluid                                                                           0.10 weight percent                                         (prepared by the Dow                                                          Corning Corporation)                                                          Tween 20 surfactant                                                                             0.03 weight percent                                         (prepared by ICI America                                                      Corporation)                                                                  One of the perfumery sub-                                                                       0.10 weight percent                                         stances as set forth in                                                       Table II of Example VI,                                                       supra                                                                         ______________________________________                                    

The perfuming substances as set forth in Table II of Example VI addaroma characteristics as set forth in Table II of Example VI which arerather intense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE XIII Conditioning Shampoos

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated to 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "COMPOSITION A".

Gafquat® 755N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "COMPOSITIONB".

The resulting COMPOSITION A & COMPOSITION B are then mixed in a 50:50 wtratio of A:B and cooled to 45° C. and 0.3 wt percent of perfumingsubstance as set forth in Table II of Example VI is added to themixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of thisblending period, the resulting material has a pleasant fragrance asindicated in Table II of Example VI.

Patents Incorporated Herein By Reference

The following patents referred to supra, are hereby incorporated hereinby reference:

U.S. Pat. No. 3,632,396

U.S. Pat. No. 3,948,818

Canadian Pat. No. 1,007,948.

What is claimed is:
 1. A mixture of compounds defined according to thestructures: ##STR130##
 2. A compound defined according to the structure:##STR131##